Ar-n-(nitro-phenyl)-tetrahydronaphthylamines and process of preparing same



cellulose esters or ethers.

Patented Jan. 7, 1936 a UNITED STATES f 2,020,148 I an N (m'rno -PHENYL)- mmanrpnomrnrnmmmss m rnocnss or ranmnmo SAME new, Charles 01pm, Spondon, near Derby, Engassignor to Celancse Corporation of America, a corporation oIDela'are No Drawing. Application January 2 5, 1930, Serial NIL-423,5Q6. InGteat Blitzinmmh. 12, 1929 v 5 clai s. (01. zli0- -128) This invention relates to the manufacture of new dyestuffs and the application thereoi and more particularly their application to made of or containing cellulose acetate or other The new dyestuffs oi the present invention are prepared by condensing ar tetrahydro-aorpnaphthylaminc, or derivatives thereof, with 111- trated aromatic compounds containing" one or 1 more labile halogen For convenience the new dyestufis be termed fl-nitro-aryl-artetrahydroaor fi-naphthylamines whether they are obtained from 'the naphthylamine itself or a derivative thereon The new dyestufls have in general greenishyellow to yellow-brownshades and are especially of value for the dyeing or otherwise colouring of materials'made otcellulose acetate or'other cellulose esters or ethers, ior'eqrample cellulose formate, propionate or butyrateor the products obtained by the treatment of alkalizcd cellulose with esterifying agents, e. g. the product known as immunized cotton" obtained with p-toluene sulpho-chloride, or inethyhethyl or benzyl cellulose or the like or containing cellulose esters or ethers mixed with other fibres. For this purpose the dyestuffs should not contain more than one sulphonic group. n H

As examples of suitable nitro aromatic compounds whichmay be condensed with the artetrahydro-aor penaphthylamines the iollow ing may be mentioned: g

zA-dinitro-cl'ilor-benzene Z-nitro-chIor-bemiene e 2-pnitro-brom-benzene 2.5-dichlor-nitro-benzene 2.4-dinitro-chlor-benzene-6wsulphonic acid 2.4-dinitro-chlor-benzene-G-carboxylic acid The following are some examples of dyestufis which may be prepared and applied according to the present invention:-

Shade on cellulose Dyestufi acetate Ar-N-(2:4- dinitro phenyl) tetrahydro -p -r Bright greenish yellow.

nophthylamino.

TH: E:

naphthylam ne.

Golden yellow.

Ar-N-(2z4-dinitro-o-sulpho-phenyl) totra- Pure yellow.

hydro-mnephthylamln Similar shades are obtained by using the mono alkyl or mono'acetyl derivatives of the tetrahy dro-naphthylamines.

For the purpose of dyeing cellulose esters or others 1 the dyestuffs .1 where sufllciently soluble may be applied in the form of their aqueous solutions or in the form of aqueous solutions of their salts. In so applying them any of the usual assistants may be employed. It insuflicientl'y soluble, the dyestuffs may be applied from aqueous suspensions or dispersions prepared by any suitable methods. Dispersions may, tor example, be obtained by grinding in the so-called colloid mills, by dissolving in a solvent and mixing with water containing or not containing dispersators or protective colloids or by treatment with dispersators for example in the manner described in prior U. S. Patents Nos. 1,618,413., 1,618 414, 1,694,413, 1,690,481, 1,716,721, 1,803,008, 1,840,572 and 1,928,647 and British Patent No. 323,788. The compositions of matter containing the relatively water insoluble dyestufls and a dispersator and/or a protective colloid are included in the present; invention.

The following examples show the best methods known to us for carrying the invention into effect, but they are of course not intended .to limit theinvention in any way:

Example 1 147 parts of ar-tetrahydro-a-naphthylamine are dissolved in 1000 parts of methylated spirit, 202 parts of 2:4-dinitro-chlorbenzene and 82 parts of anhydrous sodium acetate are added, and the whole boiled under reflux for l-l A; hours.

On cooling to normal temperature the dyestulf crystallizes out in a very good state of purity.

On recrystallizing from methylated spirits the dyestuff, ar-N- (2 4-dinitro-phen'yl) -tetrahydrou-naphthylamine, is obtained as bright orangered crystals, melting point 127-l28 C. (uncorrected), and having the formula Ha Illa Example 2 I chlor-phenyl)-tetrahydro-p-naphthylamine, is

thus obtained as red-brown crystals, melting point 124-125 C. (uncorrected), and having the probable formula Int-ample 3 To dye a bright greenish yellow shade on 10 kilos of cellulose acetate yarn in hank form:

100 grams of ar-N-(2:4-dinitrophenyl)-tetrahydro-p-naphthylamine are ground to a fine powder, and stirred into 500 grams of the sulphoaromatic fatty acid product prepared according to Example A in United States Patent No.

1,694,413. The mixture is heated until the maximum degree of dispersion is achieved, then diluted with boiling water and added through a sieve into a dye bath containing 300 litres of water. The goods are now entered and processed. the "temperature being raised in the usual manner until'the desired shade is achieved. The goods are now lifted, rinsed, and dried or otherwise treated as requisite.

Earample 4 To dye a bright yellow on 10 kilos of cellulose acetate knit fabric:-

200 grains of theproduct ar-N-(2z4-dinitro-6- sulpho-phenyl) -tet rahydro-u-naphthylamine are dissolved in 300 litres of water at 5060C. and

' the goods entered. The temperature is slowly raised to C. and the fabric processed at this temperature till the desired shade is achieved. The goods are now lifted, rinsed and dried or otherwisev treated as requisite. The term nitro-pheny asused in the claims is to be understood 'as including phenyl radicles containing other substituent groups or atoms, as for example chlorine, in addition to nitro groups, as well as phenyl radicles in which nitro groups are the only substituent groups.

What I claim and desire to secure by Letters Patent ls:' 1. Process for the production of new dyestuiis, comprising condensing a compound selected from the group consisting of ar-tetrahydro-aand p-naphthylamines and their mono-alkyl and mono-acetyl nuclear substitution derivatives with a nitrated aromatic compound of the benzeneseries containing at least one labile halogen atom.

2. Process forthe production of new dyestuffs comprising condensing an unsulphonated compound selected from the group consisting of artetrahydro-aand fi-naphthlyamines and their mono-alkyl and mono-acetyl nuclear substitution derivatives with a nitrated aromatic compound of the benzene series containing at least one labile halogen atom.

3. Process for the production of new dyestuffs comprising condensing an ar-tetrahydro naphthylamine with a nitrated aromatic compound of the benzene series containing at least one labile halogen. e

, 4. Process for the production of new dyestuffs comprising condensing an unsulphonated artetrahydro naphthylamine with a nitrated aromatic compound of the benzene series containing at least one labile halogen.

5. Ar-N- (nitro-phenyl) -tetrahydro-naphthylamines.

HENRY CHARLES OLPIN. 

